Dyed edible food casings

ABSTRACT

Dyed edible food casings, e.g., sausage casings, are produced by applying an edible dye to an edible carrier therefor, fixing the dye on the carrier by use of a protein, and admixing the carrier with an edible casing material to form an extrudable composition. That composition is then used for production of the casing by extrusion. The dye can be a water soluble dye, a fat soluble but water insoluble dye, or a water insoluble, alkali soluble dye.

This is a division of application Ser. No. 505,444 filed Sept. 12, 1974,now U.S. Pat. No. 3,943,262.

BACKGROUND

This invention relates to edible food casings, especially for sausages,which are dyed with an edible dyestuff, and to a process for themanufacture of such casings.

The invention is an improvement in, or modification of, that forming thesubject of copending application Ser. No. 340,776, filed Mar. 13, 1973,now abandoned.

Edible food casings made of a skin fiber composition of animal origin(collagen) are known especially for sausages. Such casings are beingused increasingly for the production of frankfurters and Viennasausages, and their manufacture is described, for example, in GermanPat. No. 972,854. Such collagen sausage casings range from practicallycolorless to pale yellow. In sausages where the casings in intended tobe consumed, and especially in the case of the various scaldingsausages, such as bockwurst, an increasing consumer preference towards astrongly colored sausage has become evident. Thus in some countries,such as USA, France and Great Britain, certain sausages, such as thewell-known "hot dogs" are marketed dyed red. The red dyeing is effectedtogether with the scalding or boiling process, by surface dyeing of thesausage casing, through addition of the dyestuff to the bath in whichthe filled sausage is scalded or boiled.

Such a method of dyeing has several disadvantages: First, uniform dyeingcan be obtained only with great difficulty. The casing shows regionswhich are dyed more weakly or not at all, depending on how closetogether the sausages were laying and how adequately they have beenwetted by the dyestuff liquor. Furthermore, the dyestuff tends both tobleed out and also to migrate into the sausage material. In spite ofusing the same dyestuff concentration, completely identical dyeing ofsuccessive batches is never achieved.

It has also been proposed to dye artificial sausage casings made ofextrudable material which swells in water by dissolving edible dyestuffssoluble in fat or oil and distributing the resulting solution in theform of a "fat-in-water" emulsion in the raw material of the casingsbefore they are shaped (Canadian Pat. No. 906 716, TEE-PAK).

In practice, dyed sausage casing produced in this manner have thedisadvantage that during the scalding sausage preparation, under theaction of hot air, steam, and scalding water, considerable portions ofthe dyed fats embedded in the casing material come into contact with thelargely fatty sausage composition and color it. The result is asubstantial disappearance of the coloring of the sausage casing and anundesired transfer of the dye to the periphery of the sausage material.

In said application Ser. No. 340,776, it is proposed to dye a sausagecasing of edible material such as collagen or alginate, with an edibledyestuff, which represents a significant improvement in composition withthe known dyed sausage casings as regards uniformity of dyeing andfixing the dye in the casing. The sausage casings according to said Ser.No. 340,776 are dyed with an edible, e.g., legally permitted, dyestuff(primarily a water-soluble dyestuff).

As proposed in the copending application, the dyeing may be effected byadding the dyestuff to the composition before extruding the tube, or byimmersion of the tube, or by spraying the extruded tube with an aqueousdyestuff solution. Fixing the dyestuff on or in the casing may beeffected, in the case of dyeing the extruded sausage casings, byemploying as the dyes, substances which are cross-linkable under theaction of heat, and/or the action of hardening or tanning agents. Suchagents include proteins, cellulose, cellulose derivatives, pectins,alginates and structurally similar substances. Examples of proteinswhich may be used include gelatin, casein, and collagen. Swellablecellulose derivatives such as methyl cellulose, ethyl cellulose, arealso suitable, as are gum arabic and guar gum as hardening or tanningagents similar to pectin. The quantity of any such substance added maybe from 0.1 to 2% based on the aqueous dye solution. The dye bathsproduced in this manner may be regarded as dyed colloidal solutions ofthe proteins or polymeric carbohydrates. By adding tanning agents suchas, for example, glutaraldehyde, glyoxal, or aluminum salts, the dyescan be cross-linked with the base substance of the tube, e.g., collagen.A certain degree of cross-linking and water-resistance can also beproduced without using hardening or tanning agents, by exposure to hotair at 70° to 105° C for 4 to 10 hours.

If the dyestuff is added to the composition before tube formation, avery effective method of fixing the dyestuff consists of embedding it ina hydrophobic substance, for example, a fat, and then emulsifying it inthis form into the composition to be extruded, preferably collagen. Thismethod is particularly advantageous for water-soluble food dyestuffs.

As described in the said Ser. No. 340,776 a further improvement of theefficiency of the dyestuff, in conjunction with excellent fixing, isobtained if the water soluble dyestuff is first of all applied to acarrier and the dyed carrier is then surrounded by a hydrophobicencapsulating substance. Suitable dyestuff carriers comprise allinsoluble, swellable or non-swellable materials which are edible orharmless. Preferably, a white or colorless carrier substance is used sothat the color shade is not changed by the intrinsic coloration of thecarrier. Examples of suitable carrier materials include cellulose andcellulose derivatives in the form of fibers or powders, strach powders,collagen powders and casein powders. Of course, mixtures of suchmaterials can also be employed.

Advantageously the carrier, which consists, for example, of particles ofa finely ground cellulose powder, is dyed with a relatively concentratedsolution of the dyestuff in a hydrophobic encapsulating agent and thendried. Possible hydrophobic encapsulating substances comprise all thoseoils and fats which are customarily used in the foodstuff field, forexample synthetic glyceride mixtures, sunflower seed oil, beef fat andlard. High-melting fats and waxes can also be used such as, for example,beeswax and paraffin, alone or mixed with the other fats and oils.

THE INVENTION

The present invention is based on the appreciation that the use of thedyestuff and its fixation in or on the food casing can be even furtherimproved, in comparison with techniques disclosed in said Ser. No.340,776 by applying the dyestuff to the surface of a solid carrier andsubsequently fixing the dyestuff by sequestration with a protein. Thesequestration involves the fixing of the dyestuff on the carrier so thatit is more insoluble in water and in oil. It is believed the fixationinvolves the formation of a complex between the dye and the protein.

Dyestuff suitable for this method include not only the aforementionedwater-soluble materials, but also dyestuffs soluble in fat and insolublein water or soluble in alkali. The improved properties of casings inwhich the dyestuff is fixed by sequestration (complex formation) afterit has been applied to the carrier may be demonstrated by the fact thatthe casings can be boiled in water or treated with hot fat at 100° Cwithout the slightest loss of color. By using the method of the presentinvention, the efficiency of a dyestuff, e.g., of a dyestuff soluble inoil, may be as much as doubled as compared with incorporating an oilysolution of the dyestuff directly in the base material without using acarrier.

Small quantities of proteins, e.g., gelatin solution or suspensions ofcollagen fibers or casein in water, will generally suffice to fix thedyestuff on the surface of the carrier particles. It has been found thatthe fat-soluble carotinoids such as, for example β-carotene,astaxanthin, apocarotinal, canthaxantin, and capsanthin, andalkali-soluble dyestuff, which are insoluble in water, such as, forexample, carmin, orcein, indigotine, curcumine and bixin form dyestuffcomplexes with proteins, which complexes are insoluble in water and acidand are suitable for the purposes of the invention. The proteins maysubsequently be set further by alteration of the pH or by treatment withsmall quantities of a tanning substance, such as alum, formaldehyde orother bifunctional aldehydes.

To produce a good extrudable mix, the dyestuff on the carrier obtainedas described herein may next be dispersed in an aqueous collagensuspension (for example, a 1% suspension) to fix the dyestuff on thecarrier, and this dispersion can be subsequently worked, in a Z-mixer,into the base, e.g., collagen composition, of variable dry substancecontent, appropriate for the extrusion of dyed sausage collagen tubes.

The intensity of the coloring of dyed food casings made in accordancewith the invention is surprisingly high, and it is possible to obtainsatisfactory results using only 40 to 60% of the dyestuff expenditureneeded for direct dyeing with an oil-in-water emulsion.

Dispersions of the dyestuff concentrates in, for example, 1% collagensuspensions are mutually very compatible, which makes it possible toproduce any desired shade from yellow through orange, to red or ochre tomahogany brown.

Instead of collagen as the base material, other edible casing materials,for example, polyvinyl alcohol and alginate can also by dyed inaccordance with the invention. Mixtures thereof can also be used.

The carrier material is preferably cellulose powder. It can also be woodpulp, starch powder, cellulose derivatives, e.g., methylcellulose,ethylcellulose, carboxymethylcellulose, and casein powder, collagenpowder, or a mixture of two or more of the said substances.

The dye before application to the carrier is preferably combined with ahydrophobic encapsulating agent, which can be any of such agents notedabove in the discussion of Ser. No. 340,776.

Based on the carrier, the amount of the dye can be 1 to 15, preferably 2to 10 wt.%, combined with 50 to 90 wt.%, based on the carrier ofencapsulating agent. Still based on the carrier, the amount of proteinemployed for the fixation, for example in a 1% aqueous suspension, canbe 10 to 90, preferably 25 to 50 wt.%. The fixing agent can be anaqueous suspension of the protein in which based on the water, the agentis 0.5 to 10 wt.%, preferably 1 to 5 wt.%. A 1% suspension works well.The proportion of the dye to base material, e.g. collagen paste which isdyed, can be 0.1 to 2 preferably 0.1 to 1.5 wt.% of dye based on theamount of base material (dry weight).

Thus, the invention provides a process for the production of a dyededible food casing comprising applying an edible dye to an ediblecarrier therefor in finely divided form so that the dye coats thecarrier particles, fixing the dye on the carrier particles by contactingthe coated particles with a protein, admixing the carrier with an ediblecasing material to form an extrubable composition, and extruding theresulting admixture to form the dyed casing. Desirably the dye is fixed,and is thereafter admixed with the edible casing or base material.

As noted above, by reason of the fixing, the water and fat solubility ofthe colors in the sausage casings provided by the invention is reducedto nearly absolute insolubility. When processing frankfurters or Viennasausages there is no transition of color to the sausage emulsion and nobleeding out into the scalding water.

EXAMPLE 1

3.75 g of cellulose powder are moistened with 2.00 g of ethyl acetate.3.3 g of a solution of 100 mg of β-carotene (crystalline, synthetic) in3.2 g of liquid fat (sunflower oil) is introduced into the powder, whichcan still flow, in a high speed agitator. The resulting paste isdispersed in 100 ml of a 1% aqueous collagen suspension. This prepareddye mixture is worked into 500 g of 12% collagen paste in a Z-mixer.

It is possible to produce from a collagen composition dyed in thismanner 68 g or 27.6 m of edible food casings of 23 mm calibre. Thecasings contain 0.145% carotene, are uniformly colored deep orange-redand the dye is resistant to the hot fat and water conditions encounteredin the production of frankfurter and Vienna sausages.

EXAMPLE 2

4 g of potato or rice starch are moistened with 2 g of dioxane. 3.0 g ofa 5% solution of canthaxanthin in olive oil is worked into the stillmoist powder and the resulting paste is worked into 1500 g of a collagenpaste having a solids content of 4%. In this manner, the canthaxanthinis fixed by complex formation with the collagen. The paste is extrudedinto tubular form and the extruded tube is coagulated in a coagulationbath consisting of an almost saturated aqueous solution of ammoniumsulphate and sodium chloride, after which the tube is hardened in ahardening bath containing an aqueous alum solution. It is then washed,plasticized with glycerol or sorbitol, and finally dried.

EXAMPLE 3

3.75 g of cellulose powder are moistened with 2.00 g of ethyl acetate.4.53 g of a mixture of 3.2 g of pig fat and 1.33 g of oleoresen(paprikaoleoresin or paprika extract) is introduced into the powder,which is still capable of flowing, and the resulting paste is dispersedby means of a high speed agitator into 100 ml of a 1% aqueous collagensuspension. The finished dye preparation is worked in a Z-kneader into500 g of 12% collagen paste. It is possible to produce from a collagencomposition dyed in this manner, which contains 68 g of solidsubstances, 34 m of edible sausage casings of a diameter of 21 mm. Thecasings are uniformly dyed brown-red. Under the conditions for theproduction of frankfurters and Vienna sausages they prove to beresistant to hot fat and hot water.

EXAMPLE 4

This example illustrates the production of a permanent coloring in acollagen sausage casing using a dyestuff insoluble in fat. 4.0 g of"carmine-fast" (cochineal extract) are dissolved in 200 ML of water withthe addition of 2 ml of concentrated amonia solution. 30 g of cellulosepowder are added to the bluish solution in a solvent, followed by 8 g ofcasein.

After uniform distribution of all components, dilute hydrochloric acidis added until the pH value reaches 3. The mixture is then allowed tostand for 45 minutes, after which it is introduced into and dispersed in600 ml of a 1% collagen fiber suspension in a high speed agitator. Theresulting colored paste is then worked portionwise into 3000 g of a 12%collagen paste in a Z-mixer. The dyestuff fixed to the carrier by thedyed protein confers on the 408 g of edible sausage casings of 30 mmdiameter produced from the finished collagen composition, a luminous redcolor which proves to be resistant to hot fat and hot water in thecourse of the production of frankfurters and Vienna sausages.

In the case of oxidation-sensitive dyestuffs with conjugated C--C doublebonds, such as carotinoids, the addition of an antioxidant in quantitiesof up to 5% by weight based on the dyestuff is recommended. Example ofantioxidants which may be used include vitamin E, vitamin C, citric acidand ascorbyl palmitate.

As illustrated in the foregoing examples, the dyestuff solution isdistributed on a carrier, which is preferably finely ground and shouldbe both fat- and water-insoluble, and is preferably powdered cellulose.For improved wetting of the powdered carrier with an oily dyestuffsolution of, for example, carotene, the powder is preferably wettedinitially with a polar solvent such as, for example, ethyl acetate ordioxane (Example 1 and 2, respectively).

In the case of a solution in alkali of a dyestuff such as, for example,carmine (which may be prpared with a 1% aqueous solution of 25%ammonia), the resulting solution will itself wet cellulose powderthereby obviating the need for pretreatment.

Examples of other suitable carriers are wood pulp, starch powder,cellulose derivatives, e.g., methylcellulose, ethylcellulose,carboxymethylcellulose, and casein powder, collagen powder, or a mixtureof two or more of the said substances. The swellability with water ofthe mentioned cellulose derivatives and proteins can be decreased by ahardening treatment with formaldehyde or other dialdehydes such as, forexample, glyoxal or glutaraldehyde.

Very desirable results are obtained if the volume of the dyestuffsolution applied to the carrier is so chosen in relation to the surfacearea of the carrier that a thin cohesive film of the dyestuff solutioncovers substantially the whole of said surface. For example, when thecarrier is a powder of ground cellulose fibers of which the diameter is10 to 12 μm and the mean length of the particles is 80 to 100 μm, thefilm thickness of the dyestuff may be in the order of 2 μm. If, forexample, the carrier is finely ground powder of hardened collagen of amore sphaerical shape with a diameter of 20 to 30 μm, the film thicknessof the dyeing composition is about 2 μm.

The carrier particles can be in the size range of 10 to 30 μm indiameter, preferably 10 to 15 μm, and 1 to 200 μm in length, preferably5 to 150 μm. The mean particle size of a cellulose powder can be 10 to12 μm in diameter and 20 to 150 μm in length, preferably 50 to 100 μm.

The film containing the dye is distributed over the surface of thecarrier particles as a coating of thickness 0.5 to 5 μm, preferably 1 to3 μm.

What is claimed is:
 1. A dyed edible food casing produced by the processwhich comprises:a. applying an edible dye to an edible carrier thereforin finely divided form so that the dye coats the carrier particles, b.fixing the dye on the carrier particles by contacting the coated carrierparticles with a protein from the group consisting of gelatin, collagenand casein for complex formation whereby the dye becomes fixed on thecarrier, and thereafter, c. admixing the carrier coated with the dyewith an edible casing material to form an extrudable composition, and,d. extruding the resulting admixture to form the dye casing.
 2. A dyededible food casing of claim 1, the casing containing a quantity of dyein the range of from 0.1 to 2 wt.%.
 3. A dyed edible food casing ofclaim 1, wherein the edible dye is a water-soluble or water-insoluble,alkali-soluble dyestuff.
 4. A dyed edible food casing of claim 3,wherein said edible dye is at least one of carmin, orcein, indigotin,curcumin and bixin.
 5. A dyed edible food casing of claim 1, whereinsaid carrier material comprises cellulose.
 6. A dyed edible food casingof claim 5, wherein said casing material comprises collagen, polyvinylalcohol, or alginate.
 7. A dyed edible food casing of claim 1, whereinsaid casing material comprises collagen, polyvinyl alcohol, or alginate.8. A dyed edible food casing of claim 1, wherein the edible dye combinedwith an edible hydrophobic encapsulating agent is applied to thecarrier.
 9. A dyed edible food casing of claim 1, the amount of dyebeing 0.1-2 weight percent of the dry weight of said extrudablecomposition, the amount of dye further being 1-15 weight percent of thecarrier, and the amount of protein being 10-90 weight percent of thecarrier.
 10. A dyed edible food casing of claim 1, wherein the edibledye is a fat-soluble carotinoid.
 11. A dyed edible food casing of claim1, wherein the protein is collagen.
 12. A dyed edible food casing ofclaim 1, wherein the protein is casein.
 13. A dyed edible food casing ofclaim 1, wherein said edible casing material is collagen.
 14. A dyededible food casing of claim 13, wherein said protein is collagen.
 15. Adyed edible food casing of claim 13, wherein said protein is casein. 16.A process for the production of a dyed edible food casing comprising:a.applying an edible dye to an edible carrier therefor in finely dividedform so that the dye coats the carrier particles, b. admixing thecarrier coated with the dye with an edible protein casing material tofix the dye on the carrier particles by complex formation whereby thedye becomes fixed on the carrier and to form an extrudable composition,and c. extruding the resulting admixture to from the dyed casing. 17.Process of claim 16, wherein the protein casing material is collagen.18. Product produced by the process of claim 16.